Kirchberg Henning, Nitzan Abraham
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA.
Entropy (Basel). 2023 Aug 16;25(8):1218. doi: 10.3390/e25081218.
We considered discrete and continuous representations of a thermodynamic process in which a random walker (e.g., a molecular motor on a molecular track) uses periodically pumped energy (work) to pass sites and move energetically downhill while dissipating heat. Interestingly, we found that, starting from a discrete model, the limit in which the motion becomes continuous in space and time (N→∞) is not unique and depends on what physical observables are assumed to be unchanged in the process. In particular, one may (as usually done) choose to keep the speed and diffusion coefficient fixed during this limiting process, in which case, the entropy production is affected. In addition, we also studied processes in which the entropy production is kept constant as N→∞ at the cost of a modified speed or diffusion coefficient. Furthermore, we also combined this dynamics with work against an opposing force, which made it possible to study the effect of discretization of the process on the thermodynamic efficiency of transferring the power input to the power output. Interestingly, we found that the efficiency was increased in the limit of N→∞. Finally, we investigated the same process when transitions between sites can only happen at finite time intervals and studied the impact of this time discretization on the thermodynamic variables as the continuous limit is approached.
我们考虑了一个热力学过程的离散和连续表示,其中一个随机漫步者(例如,分子轨道上的分子马达)利用周期性泵入的能量(功)通过位点,并在散热的同时能量下坡移动。有趣的是,我们发现,从一个离散模型开始,运动在空间和时间上变得连续(N→∞)的极限不是唯一的,并且取决于在该过程中假设哪些物理可观测量不变。特别是,人们可以(通常那样做)选择在这个极限过程中保持速度和扩散系数不变,在这种情况下,熵产生会受到影响。此外,我们还研究了在N→∞时以修改后的速度或扩散系数为代价使熵产生保持恒定的过程。此外,我们还将这种动力学与克服反向力的功相结合,这使得研究过程离散化对将功率输入转换为功率输出的热力学效率的影响成为可能。有趣的是,我们发现在N→∞的极限下效率提高了。最后,我们研究了位点之间的跃迁只能在有限时间间隔内发生的相同过程,并研究了在接近连续极限时这种时间离散化对热力学变量的影响。